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Possibility of reducing the coordinated dinitrogen into ammonia and hydrazine using [Ru-L] (L = triamidoamine) and FLP-H\(_{2}\): A DFT study

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Abstract

DFT studies have been executed on a hypothetical Ru-triamidoamine complex to understand the possibility of synthesizing ammonia and hydrazine from the dinitrogen at normal temperature and pressure in heptane. In this present study, we utilized the \(\hbox {H}_{2}\) in the form of FLP-\(\hbox {H}_{2}\) complex and reacted with Ru-triamidoamine complex. We have added three \(\hbox {H}^{+}\) and \(\hbox {H}^{-}\) parts of FLP-\(\hbox {H}_{2}\) to the Ru complex in a stepwise manner as an alternate way to yield \(\hbox {NH}_{3}\)/\(\hbox {N}_{2}\hbox {H}_{4}\). The catalytic cycle for the formation of \(\hbox {NH}_{3}\) and \(\hbox {N}_{2}\hbox {H}_{4}\) were found to be energetically feasible. We have also observed some thermodynamically feasible six coordinate [M]-H intermediates.

Graphical Abstract

DFT studies were carried out on the possibility of synthesis of ammmonia and hydrazine from the dinitrogen using Ru-triamidoamine complex via FLP-\(\hbox {H}_{2}\) under normal experimental conditions. The calculated free energies revealed that the formation of all the intermediates and the transition states are thermodynamically viable. Furthermore, our calculations predicted that the formation of ammmonia is more feasible than hydrazine.

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Acknowledgements

C. S. thanks the Science and Engineering Research Board (EMR/2014/000623), New Delhi, India for the financial support.

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  1. Catalysis and Energy Laboratory, Department of Chemistry, Pondicherry University, Kalapet, Puducherry, 605 014, India

    Thayalaraj Christopher Jeyakumar, Sambath Baskaran & Chinnappan Sivasankar

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  1. Thayalaraj Christopher Jeyakumar
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Correspondence to Chinnappan Sivasankar.

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Christopher Jeyakumar, T., Baskaran, S. & Sivasankar, C. Possibility of reducing the coordinated dinitrogen into ammonia and hydrazine using [Ru-L] (L = triamidoamine) and FLP-H\(_{2}\): A DFT study. J Chem Sci 130, 57 (2018). https://doi.org/10.1007/s12039-018-1460-1

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